The Gaseous

State
Chapter 5

Agenda
Preliminaries
Properties of Gases
Gas Laws
Ideal Gas Law
Daltons Law
Kinetic Molecular Theory
Real Gases

Coverage in Tro et al.

5.2 Pressure: The Result of Molecular Collisions

(exclude manometers)
5.3 The Simple Gas Laws
5.4 The Ideal Gas Law
5.5 Applications of the Ideal Gas Law
5.6 Mixtures of Gases and Partial Pressures
5.7 Gases in Chemical Reactions: Stoichiometry
Revisited
5.8 Kinetic Molecular Theory: A Model for Gases
5.9 Mean Free Path, Diffusion, and Effusion of Gases
5.10 Real Gases
3

Preliminaries

Pressure concept at
molec level
px

Momentum transfer:
Particle p = -px -px = -2px
wall p = +2px
Force:
over a time interval, t,
momentum, <p>, is transferred
to the wall from large number of
collisions
px
F = <p>/t

Pressure:
P = F/A

py

py

p
5

Pressure units
Pressure = force per unit area

SI Unit
1 Pa = 1 Nm-2 = 1 kgm-1.s-2

Related units
1 kPa = 1000 Pa
1 bar = 105 Pa (exactly)
1 atm = 101,325 Pa

Other pressure units

torr (name) or Torr (unit)
Pressure measured with barometer
Atmospheric P pushes Hg up tube
Hg level rises to point where P due
to Hg weight balances atmos. P
Measure height (h) of Hg column

P = gh
1 Torr = P required to raise Hg
column by 1 mm
1 bar = 750.0 Torr

LC: Pressure Units

The normal atmospheric pressure at the
top of Mt Everest (8,848 m) is about 0.308
atm. What is that in bar if 1 atm =
101,325 Pa?
A. 0.302
B. 0.312
C. 0.322
D. 0.332

LC: Pressure Units

Some Terms To Memorize

Standard temperature and pressure (STP):
0C (273.15 K) and 1 bar
Room temperature and pressure (RTP):
25C (298.15 K) and 1 bar
Know these terms (there are only two)

10

Properties of
Gases

11

Properties of Gases
Expand to fill the volume of the container
Highly compressible
No phase separation in mixtures
Molecules only weakly interact
Gaseous substances at RTP:
Some molecular elements (e.g. Ar, Cl2, F2, N2,
etc.)
Many small molecules (e.g. HCl, NH3)

12

13

14

The Gas Laws

15

Boyles Law
The volume of a gas maintained at constant

temperature is inversely proportional to the

pressure
i.e., at constant moles and T,

V = C/P
where C is a constant

OR:

PfVf = PiVi

16

Boyles Experiment:

17

18

Charless Law
The volume of a gas maintained at constant

pressure is directly proportional to the

absolute temperature (in kelvins)

V CT (constant moles and P)

or

Vf
Tf

Vi
Ti
19

20

21

Blue balloon dipped in liquid nitrogen

22

LC: Charless Law

A helium balloon with a volume of 2.00 L at
22.0C is dropped into a large container of
liquid nitrogen (196.0C). The final volume of
the gas in the balloon is:
A.
B.
C.
D.

0.224 L
0.522 L
7.65 L
17.8 L
23

Solution: Charless Law

A helium balloon with a volume of 2.00 L at
22.0C is dropped into a large container of
liquid nitrogen (196.0C). The final volume of
the gas in the balloon is:
Vi = 2.00 L
Ti = (22.0 + 273.15) K = 295.2 K
Tf = (-196.0 + 273.15) K = 77.2 K
Tf
2.00 L 77 K
V f Vi
Vf
0.522 L
Ti
295 K
24

Avogadros Law
Equal volumes of gases at the same

temperature and pressure contain equal

numbers of molecules
V = const. n
At 25C and 1 bar pressure, V/n 25 L/mol

25

26

Ideal Gas Law

Putting it all together

27

Ideal Gas Law

Combines all the gas laws:
PV = nRT
R is the gas constant:
R = 8.314 J K-1mol-1 = 8.3145 Pa m3 mol-1 K-1
= 0.08314 L bar mol-1 K-1
(= 0.08206 L atm mol-1 K-1)
So,
PV = const. at constant T, n (Boyles Law)
V T at constant P, n (Charless Law)
V n at constant T, P (Avogadros Law)
28

Pictures and reality

O2 collision diameter (c.d.) = 3.467

Window volume: 6 c.d. wide 1 c.d. deep
r2d = 1178 3

V = 1.17810-27 m3

Density: 8.5/1178 3 or 7.21027 m-3

n/V = 1.2104 molm-3
Pressure at 298K: ~300 bar!
29

Example

30

Example

31

LC: Ideal Gas Law

An empty aerosol can has a volume of 0.406 L
and contains 0.025 mol of a propellant gas.
What is the pressure of the gas at 25.0C?
(R=0.083145 Lbarmol1K1)
0.13 bar
B. 1.3 bar
C. 1.5 bar
D. 1.5102 bar
A.

32

Solution: Ideal Gas Law

33

Ideal Gas Law (IGL)

Problems
Usually at least one variable fixed
Fixed variables are your handle
Start by figuring out what is fixed and what is

changing

34

Example
3.29 mol of ideal gas are contained inside a
cylinder-and-piston system under an external
pressure 1.01 bar, which is balanced by the
pressure of the ideal gas. Calculate the volume
change as the system is heated from 300 K to 500
K. (R=0.083145 L bar/mol/K)
What is changing?
Volume (to find) and temperature (300-500 K)

What is fixed?
Moles (sealed by piston) & pressure (1.01 bar)
Suggests Charless Law
35

Apparatus
1.01bar

1.01bar

500K
300K
36

Answer
V = Vf - Vi
Vi = nRTi/P (one unknown)
= (3.29 mol)(0.083145 L bar/mol/K)(300 K)
(1.01 bar)
= 81.2 L
by Charless Law, Vf = Vi(Tf/Ti)
Vf = (81.2 L)(500 K/300 K) = 135.4 L
V = Vf - Vi = 135.4 L - 81.2 L = 54 L
37

Using the handle

A weather balloon ascends to an altitude at
which T=226 K and P=0.26 bar. If the balloon
had an initial volume of 7.2 L at sea level
(T=288 K; P=1.00 bar), what is the volume at
the high altitude? (R=0.083145 L bar/mol/K)
A. 9.6 L
B. 14 L
C. 22 L
D. 30L
38

Example 2
What is changing?
T (293 to 250K), V (7.2 L to ?) and P (1.00 to 0.45 bar)
What is constant?
Moles (sealed in a baloon)

ni = nf
PiVi/(RTi) = PfVf/(RTf)
Vf = ViPiTf/(PfTi)
Vf = (7.2 L)(1.00 bar)(226 K)
(0.26 bar)(288 K)
Vf = 22 L (Answer C)
39

Application: Finding Molar Mass

A 536-mL glass bulb is filled with a pure gas at 294
K and 1.01 bar pressure. The mass of the gas is
1.59 g. What is the molar mass? (R=0.083145 L
bar/mol/K)

How can we relate molar mass (M) to PV=nRT?

Through the moles (n)
M = m/n (molar mass is mass of one mole of

substance)
We can substitute n = m/M
40

Application: Finding Molar Mass

PV = nRT and n=m/M
PV = mRT/M
Rearranging for M:
M = mRT/(PV)

M = (1.59 g)(0.083145 Lbar/mol/K)(294 K)

(1.01 atm)(0.536 L)
= 71.8 g mol-1

41

LC: Finding Molar Mass

A 25.0-mL glass bulb is filled with a pure gas
at 25C and 380 Torr pressure. The mass of
the gas is 42.8 mg. What is the molar mass?
(R = 0.083145 L bar/mol/K; 1 bar = 750.0
Torr)
A.
B.
C.
D.

41.9 g/mol
83.7 g/mol
167 g/mol
7.02103 g/mol

42

Solution: Finding Molar

Mass
A 25.0-mL glass bulb is filled with a pure gas at
25C and 380 Torr pressure. The mass of the
gas is 42.8 mg. What is the molar mass?
P = 0.507 bar; T = 298 K; V=0.025 L; m
=0.0428 g

M = (0.0428 g)(0.083145 L bar/mol/K)(298 K)

(0.507 bar)(0.0250 L)
= 83.7 g mol-1
43

Finding M from Gas

Density
In the previous example we substituted the
mass and molar mass for n to get
M = mRT/(PV)
Note that m/V = (rho = the density of the
gas)
M = RT/P
Molar mass data can be converted to density
data and vice versa
44

Example
Air is a mixture of N2, O2, Ar, and other gases;
therefore, it does not have a well-defined molar
mass. However, the average molar mass of air
is approximately 29.0 g/mol.
What is the density of air at room temperature
and pressure? (R=0.083145 L bar/mol/K)
= MP/(RT)
=
(29.0 g/mol)(1.00 bar)
.
(0.083145 L bar mol-1 K-1)(298 K)
= 1.19 g/L
45

Daltons Law
Mixing it up

46

Daltons Law of Partial Pressures

P of a gas mixture = sum of the pressures that the

components would exert individually if separated.

For a mixture of N components,
P = P 1 + P 2 + P 3 + + PN
For ideal gases, P1 = n1RT/V, etc.
P = (n1+n2+n3++nN)RT/V

47

48

49

Example
What is the P of 10.0 g of O2 and 6.00 g of C2H4
in a 12.0 L bulb at 298 K? (MO2 = 32.0 g/mol;
MC2H4 = 28.1 g/mol)
ANS:
nO2 = (10.0 g)/(32.0 g/mol) = 0.312 mol
nC2H4 = (6.00 g)/(28.1 g/mol) = 0.213 mol
P = (nO2 + nC2H4)RT/V
P = (0.312 + 0.213)(0.083145)(298)/(12.0)
= 1.08 bar
50

LC: Partial Pressures

What is the total pressure of a mixture of 1.570
mol of CO and 0.870 mol NO2 in a 25.0 L
container at 25C?
(R=0.083145 L bar/mol/K; 0C = 273.15 K)
A.
B.
C.
D.

0.203 bar
1.54 bar
2.42 bar
242 bar
51

Solution: Partial
Pressures

52

Mole fraction
Partial pressure of gas A can be expressed in

terms of the mole fraction of A, A:

PA = APtotal
From Daltons law:
Ptotal = (PA + PB ++ PN) = ntotalRT/V
and
PA = nART/V
so
PA/Ptotal = nA/ntotal = A
53

Collecting Gases Over

Water

ANDwatervapour
ca.20mbar
dependsontemp.

54

LC: Gases Over Water

A 41.4 mL sample of a unknown pure gas is
collected over water at 25.0C and 769 Torr
atmospheric pressure. What is the partial
pressure of the unknown gas? (P H2O = 23.77
Torr; 1 bar = 750.0 Torr)
A.
B.
C.
D.

0.032 bar
0.994 bar
1.03 bar
1.14 bar
55

Solution: Gases Over

Water
A 41.4 mL sample of a unknown pure gas is
collected over water at 25.0C and 769 Torr
atmospheric pressure. What is the partial
pressure of the unknown gas? (P H2O = 23.77
Torr; 1 bar = 750.0 Torr)
ANSWER: B
Pgas = (769 Torr - 23.77 Torr)/750 Torrbar-1
= 0.994 bar
56

A better example
A sample containing CaCO3 is decomposed under
high temperature, producing CO 2 which is collected
over water. The volume of gas collected is 34.1 mL
at 22C and 756 Torr atmospheric pressure.
How many moles of CO2 were produced?
What mass of CaCO3 (100.1 g/mol) was present in
the original sample?
PH2O = 19.8 Torr
1 bar = 750.0 Torr
R = 0.083145 Lbarmol-1K-1
57

Answer (part 1)
By Daltons Law: P = PH2O + PCO2 = 756 Torr
PH2O = 19.8 Torr PCO2 = 736 Torr
750 torr = 1 bar PCO2 = 0.981 bar
nCO2 = PCO2V/(RT)

(0.981 bar)(34.110-3 L)
.
(0.083145 Lbarmol-1K-1)(295 K)
= 1.3510-3 mol

58

Answer (part 2)
Need a balanced chemical equation:

CaCO3 (s) CaO (s) + CO2 (g)

So, 1 mol CaCO3 produces 1 mol CO2

nCaCO3 = nCO2 (1 mol CaCO3/1 mol CO2)

= 1.36 10-3 mol
mCaCO3 = (1.36 10-3 mol)(100.1 g/mol)

= 0.136 g
59

Kinetic Molecular
Theory
How a molecular model explains gas behaviour

60

Postulates of the theory

Gases modelled as a collection of molecules
Gas molecules are in continuous, random

motion
Volume of gas >> volume of molecules
Average kinetic energy is proportional to
temperature
Does not depend on chemical identity

Collisions are elastic

Intermolecular forces are negligible
61

Molecular Picture of Gas Pressure

px

Momentum transfer:
Particle p = -px -px = -2px
wall p = +2px
Force:
over a time interval, t,
momentum, <p>, is transferred
to the wall from large number of
collisions
px
F = <p>/t

Pressure:
P = F/A

py

py

p
62

Gas Laws Explained

Boyles Law
If V (at const. T), collision frequency , so P
Charless Law
If T , collision frequency , so P but P is

constant so V instead

Avogadros Law
If n (at const. P & T), collision frequency , so P
Daltons Law
Molecules do not interact
Average energy of molecule depends solely on T
63

Ideal gas law

Can be derived (roughly) using postulates
You can look it up in the book if you are

interested

64

Molecular Speeds
We will cover molecular speeds in the

following slides
Will not cover equation 5.26
Will not cover section 5.9 MFP, Diffusion,
Effusion
You will be expected to interpret the graphs
that follow

65

Molecular Speeds and

Temp

66

Molecular Speeds and

Mass

67

LC: Kinetic Molecular

Theory
Which of the following second period gases
would have molecules traveling at the slowest
average speed at 25C?
N2
B. O2
C. F2
D. All these gases will have the same average
speed
A.

68

LC: Kinetic Molecular

Theory
Lets imagine that you have a magic radar gun that
can clock a single molecule in a gas mixture at 25C.
You pick one N2 molecule, one O2 molecule and one
F2 molecule from the mixture and measure their
speeds. Which has the highest speed?
A. N2
B. O2
C. F2
D. Theyre all the same
E. Not enough information
69

Real Gases
Adding molecular volumes and attractions to the
theory

70

Real Gases
Ideal gases are theoretical:
Molecules occupy no space
Molecules do not attract one another
For ideal gases,

PV
1
nRT

Real gases approximate ideality at high T &

low P

71

Real Gas Behaviour

Negative deviations: attractive forces
Positive deviations: molecular volumes

72

Effects of Temperature on N2 Gas

73

Van der Waals Gas

Equation

74

Van der Waals Example

75

Van der Waals Example

76

Summary
Know your gas laws (esp. IGL)
Applications & extensions of IGL
Collecting gases over water
Finding the molar mass

Kinetic Molecular Theory Know and understand it

Be able to interpret graphs of speed distributions
Real gases deviate from ideal behaviour because of
molecular interactions
molecular volumes

Know vdW equation & how to interpret non-ideal

graphs
77

Practice
Review questions 1, 4, 6, 8-14, 17-24.
Problems by topic 25, 31, 33, 35, 37, 45, 49,

51, 53, 55, 57, 61, 65, 73, 77, 79, 83, 85, 87,
91, 93, 99, 119, 129, 135.

78